Heteryl-azo-phenyl disperse dyestuffs containing a z-substituted benzolyloxyalkyl radical, wherein z is 2-cyanovinyl 2-cyanoethyl or 2-chloro-2-cyanoethyl

ABSTRACT

A dyestuff of the formula: ##STR1## in which A is thiazolyl, isothiazolyl, benzothiazolyl, benzisothiazolyl, thiadiazolyl, thienyl, or imidazolyl which is unsubstituted or substituted by one to three substituents selected from chlorine, bromine, methyl, phenyl, nitro, cyano, thiocyano, acetyl, carbalkoxy containing 2 to 5 carbon atoms and alkylsulfonyl containing 1 to 4 carbon atoms; 
     X is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, formylamino, acetylamino, propanoylamino, benzoylamino or cinnamoylamino; 
     Y is hydrogen, methyl, ethyl, methoxy or ethoxy; 
     R is hydrogen, alkyl containing 1 to 4 carbon atoms or the group of formula: ##STR2##   said alkyl being unsubstituted or substituted by one hydroxy, alkoxy containing 1 to 4 carbon atoms, phenoxy, acetyloxy, cyano, alkylsulfonyl containing 1 to 4 carbon atoms, carbalkoxy containing 2 to 5 carbon atoms or alkoxycarbonyloxy containing 2 to 5 carbon atoms; 
     N is equal to 1, 2 or 3; and 
     Z is 2-cyanovinyl, 2-cyanoethyl or 2-chloro-2-cyanoethyl and which are useful as dispersion dyestuffs for dyeing and printing fibers of fibrous materials which are based on organic substances with high molecular weight, are hydrophobic and are wholly or partially synthetic.

REFERENCE TO A RELATED APPLICATION

This is division of application Ser. No. 495,718 filed Aug. 6, 1974 now U.S. Pat. No. 3,987,027 the entire disclosure of which is relied on herein.

The present invention relates to new azo compounds which are scarcely soluble in water and can be used as dispersion dyestuffs for dyeing and printing fibres or fibrous materials which are based on organic substances with high molecular weight, are hydrophobic and are wholly or partially synthetic.

According to the present invention dyestuffs are provided of the general formula: ##STR3## in which m is equal to 0 or 1, n is equal to 1, 2 or 3, preferably 2, A represents the residue of an aromatic or heterocyclic diazotisable amine devoid of any solubilising acid groups such as sulphonic or carboxylic groups, the benzene ring B is unsubstituted or substituted by one or two atoms of chlorine or bromine or methyl, ethyl, methoxy, ethoxy or acylamino groups, X represents a hydrogen or chlorine atom or a methyl, ethyl, methoxy, ethoxy or acylamino group, Y represents a hydrogen atom or a methyl, ethyl, methoxy or ethoxy group, R represents a hydrogen atom, a mono substituted or unsubstituted alkyl group, or a group of the formula: ##STR4## and Z represents a 2-cyano-vinyl residue, a 2-cyano-ethyl residue or a 2-chloro-2-cyano-ethyl residue fixed in the ortho, meta or para postion.

Examples of residue A are phenyl, naphthyl, thiazolyl, benzothiazolyl, benzisothiazolyl, thienyl, thiadiazolyl and imidazolyl. These residues may have from one to three substituents such as, for example, chlorine or bromine atoms or the nitro, cyano, thiocyano, acyl, carbalkoxy containing two to five carbon atoms or alkylsulphonyl groups containing 1 to 4 carbon atoms.

The alkyl group, which may be represented by R or which is part of the alkylsulphonyl groups possibly present on the A residue preferably contains 1 to 4 carbon atoms. The carbalkoxy group possibly present on the A residue preferably contains 2 to 5 carbon atoms.

The acyl residue of the acylamino groups which are possibly present on the B ring or may be represented by X, may be that of an aliphatic acid with a low molecular weight, such as for example formyl, acetyl or propanoyl, or that of an aromatic acid, for example benzoyl, or of an araliphatic acid, for example, cinnamoyl.

The acetyl group may be mentioned more particularly as an acyl residue which is possibly present on the A residue.

The hydroxy, alkoxy containing one to four carbon atoms, phenoxy, acyloxy, especially acetyloxy, nitrile, alkylsulphonyl, containing one to four carbon atoms, carbalkoxy, containing two to five carbon atoms, alkoxycarbonyloxy groups containing two to five carbon atoms may be mentioned as possible substituents of the alkyl group which may be represented by R.

The dyestuffs of formula (I) may be prepared for example by coupling the diazo derivative of an amine of the formula: ##STR5## with an ester of the formula: ##STR6## or with an alcohol of the formula: ##STR7## and, in this latter case, subsequently esterifying the dyestuff thus obtained of the formula: ##STR8## for example by means of an acid chloride of the formula: ##STR9##

In formulae (III) to (VII), m, n, A, B, R, X, Y and Z have the same meanings as given above.

The amine of formula (III) may be diazotised for example in a known manner by means of sodium nitrite in a hydrochloric or sulphuric medium or by means of nitrosyl sulphuric acid mixed with sulphuric acid or possibly a carboxylic acid such as acetic or propionic acid, at a temperature of approximately 0° C.

The coupling with the ester (IV) or with the alcohol (V) may also be effected for example in a known manner in a neutral or acid aqueous medium at a temperature of from 0° C. to 5° C.

The dyestuff of formula (VI) is preferably esterified by means of the acid chloride of formula (VII) in an inert organic solvent, in the presence of a proton acceptor such as for example pyridine, piperidine or a trialkyl amine such as triethyl amine. Examples of inert organic solvents are halogenated hydrocarbons such as methylene chloride, trichlorethylene or chlorobenzene, ketones such as acetone or methyl ethyl ketone and ethers such as diethyl ether, dioxan and methoxy benzene.

The esters of formula (IV) are new products and, as such, form part of the invention. They may be prepared for example, by esterifying the alcohol of formula (V) by means of an acid chloride of formula (VII) under the same conditions as those given above for the esterification of the dyestuffs of formula (VI).

The acid chlorides of formula (VII) may be prepared for example by reacting thionyl chloride with the corresponding acids of the formula: ##STR10## wherein Z has the same meaning as that given above.

The acids of formula (VIII), in which Z represents the 2-chloro 2-cyano ethyl residue (--CH₂ --CHCl--CN), may be prepared, for example, by the Meerwein reaction between acrylonitrile and the diazonium chloride of 2-,3- or 4-amino benzoic acid. By means of a dehydro halogenation process with an alkaline agent, the acids of formula (VIII) are then obtained, in which Z represents the 2-cyano vinyl residue. The acids of formula (VIII), in which Z represents the 2-cyano ethyl residue, may be obtained for example by reducing (2-chloro-2-cyano ethyl)benzoic acids.

The new dyestuffs of formula (I), and more particularly those in which m is equal to zero, Y represents a hydrogen atom, X represents a hydrogen or chlorine atom or a methyl or acetylamino group, R represents an ethyl or β-cyanoethyl group and n is equal to 2, are remarkable disperse dyestuffs which are highly suitable for dyeing and printing fibres and fabrics based on aromatic polyesters or cellulose triacetate. Some of these dyestuffs are also suitable for dyeing cellulose diacetate and polyamides. Before they are used, it is recommended that they be converted into tinctorial preparations, i.e., that they be pre-dispersed with dispersing agents such as soap, the residual lyes of sulphite cellulose, the products resulting from condensing naphthalene-sulphonic acids with formaldehyde, in particular the dinaphthyl-methane-disulphonate, the sulphonated esters of succinic acid, the products obtained by condensing cresols with formaldehyde and naphtholsulphonic acids.

Polyester fibres may be dyed in the presence of carriers at temperatures ranging from 80° C. to 125° C. or without a carrier under pressure between 100° C. and 140° C. They may also be foularded or printed with aqueous dispersions of the new dyestuffs which are then fixed at 140° C. to 220° C.

The dyestuffs of formula (I) have excellent affinity for these fibres which they dye in shades which are very fast, particularly to sublimation and light.

Compared with the close known dyestuffs of formula (I), in which the residue ##STR11## is replaced by an acetyl, benzoyl, p-chlorobenzoyl or cinnamoyl residue, the new dyestuffs of the invention generally have superior fastness to sublimation whilst retaining an excellent tinctorial affinity.

The invention is illustrated by the following Examples, in which the parts indicated are parts by weight unless otherwise mentioned.

EXAMPLE 1 Preparation of 2-(2-chloro-2-cyano ethyl) benzoic acid

274 parts of anthranilic acid are mixed with 650 parts of hydrochloric acid (density 1.15) and 560 parts of crystallizable acetic acid. The mixture is cooled externally to 0° C. by means of a brine, then diazotised by means of 138 parts of sodium nitrite. The solution of the diazo derivative is then poured, whilst being stirred, into a mixture of 190 parts of acetone and 370 parts of acrylonitrile, at the same time as the solution of 6 parts of cuprous chloride in 50 parts of hydrochloric acid (density 1.08). The reaction is exothermic. After the diazonium chloride has disappeared and after decantation and crystallization in water, 330 parts of a product are obtained which has a melting point of 116°-117° C. and which is recrystallized in xylene. 314 parts of 2-(2-chloro-2-cyanoethyl) benzoic acid are obtained. M.P.: 119°-120° C.

    ______________________________________                                         Elementary Analysis:                                                                            C %     H %     N %   Cl %                                    ______________________________________                                         Calculated for C.sub.10 H.sub.8 NC.sub.2 Cl                                                     57.28   3.82    6.68  16.95                                   Found            57.44   3.83    6.45  16.79                                   ______________________________________                                    

By operating in the same manner using 3-amino or 4-amino benzoic acids, the meta (M.P.: 112°-113° C.) or para (M.P.: 160°-162° C.) isomers are obtained with yields of 65% and 85% respectively.

EXAMPLE 2 Preparation of 2-(2-chloro-2-cyanoethyl) benzoyl chloride

209.5 parts of 2-(2-chloro-2-cyanoethyl) benzoic acid are made into a paste in 220 parts of toluene and 125 parts of thionyl chloride and the mixture is refluxed until the acid completely dissolves. Then the surplus thionyl chloride and toluene are eliminated under reduced pressure. 2-(2-chloro-2-cyanoethyl) benzoyl chloride is obtained which is liquid at normal temperature.

By operating in the same manner using the meta or paraisomers of 2-(2-chloro-2-cyanoethyl) benzoic acid one obtains 3-(2-chloro-2-cyanoethyl) benzoyl chloride or 4-(2-chloro-2-cyanoethyl) benzoyl chloride respectively.

EXAMPLE 3 Preparation of 4-(2-cyanovinyl) benzoic acid

120 parts of potassium hydroxide are dissolved in 240 parts of methanol and this solution is poured slowly into a mixture of 209.5 parts of 4-(2-chloro-2-cyanoethyl) benzoic acid and 400 parts of methanol. The dehydrohalogenation reaction is very exothermic. Reflux is maintained for 30 minutes. The potassium salt of 4-(2-cyanovinyl) benzoic acid precipitates. It is filtered when cold and taken up in an acid medium to obtain the free acid. Thus, 160 parts of crude 4-(2-cyanovinyl) benzoic acid are obtained which are purified by sublimation under reduced pressure at about 190°-200° C. They are also sublimed under normal pressure at about 270° C.

    ______________________________________                                         Elementary Analysis:                                                                             C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.10 H.sub.7 NO.sub.2                                                         69.36    4.05     8.09                                       Found             68.04    4.15     7.88                                       ______________________________________                                    

By operating in the same manner the ortho or meta isomers may be obtained.

EXAMPLE 4 Preparation of 4-(2-cyanovinyl) benzoyl chloride

17.3 parts of 4-(2-cyanovinyl) benzoic acid are made into a paste in 80 parts of thionyl chloride and the mixture is refluxed for 15 minutes. Then the surplus thionyl chloride is eliminated under reduced pressure and the 4-(2-cyanovinyl) benzoyl chloride, which is thus obtained, is purified by being recrystallized in xylene. M.P.: 154° C.

    ______________________________________                                         Elementary Analysis:                                                                            C%      H %     N %   Cl %                                    ______________________________________                                         Calculated for C.sub.10 H.sub.6 NOCl                                                            62.75   3.14    7.32  18.55                                   Found            63.07   3.18    7.33  18.22                                   ______________________________________                                    

The ortho and meta isomers are prepared in the same manner.

EXAMPLE 5 Preparation of 4-(2-cyanoethyl) benzoic acid

100 parts of zinc powder are gradually added to a solution of 209.5 parts of 4-(2-chloro-2-cyanoethyl) benzoic acid in 500 parts of glacial acetic acid. The temperature rises quickly up to reflux and is maintained for approximately one hour. The solution is filtered when hot so as to eliminate the insoluble matter, then the filtrate is diluted with 1,000 parts of water and the precipitate formed is isolated. Thus 122 parts of 4-(2-cyanoethyl) benzoic acid are obtained. M.P.: 182° C.

    ______________________________________                                         Elementary Analysis:                                                                             C %      H %      N %                                        ______________________________________                                         Calculated for C.sub.10 H.sub.9 NO.sub.2                                                         68.57    5.14     8.00                                       Found             68.37    5.09     7.93                                       ______________________________________                                    

By operating in the same manner, the 2-(2-cyano ethyl) benzoic acid (ortho isomer) and the 3-(2-cyano ethyl) benzoic acid (meta isomer) may be prepared.

EXAMPLE 6 Preparation of 4-(2-cyanoethyl) benzoyl chloride

A mixture of 17.5 parts of 4-(2-cyanoethyl) benzoic acid and 120 parts of thionyl chloride are refluxed for 15 minutes. The surplus thionyl chloride is then eliminated under reduced pressure and the 4-(2-cyanoethyl) benzoyl chloride is obtained which is liquid at atmospheric temperature.

The ortho and meta isomers may be prepared in the same manner using the corresponding acids.

EXAMPLE 7

179 parts of N-ethyl N-hydroxyethyl metatoluidine are dissolved in 240 parts of acetone and 120 parts of triethylamine. 274 parts of 2-(2-chloro-2-cyanoethyl) benzoyl chloride are introduced gradually. The reaction is exothermic. The mixture is maintained at reflux for approximately 30 minutes. The ester of the formula: ##STR12## which is thus formed may be isolated by decantation in water. The reaction mixture may also be used as such for the subsequent coupling process.

EXAMPLE 8

0.7 parts of sodium nitrite is dissolved in 15 parts of sulphuric acid at 63° Be, then 1.63 parts of 2-amino-5-nitrobenzonitrile are introduced slowly. The solution of the diazo derivative is then poured onto 100 parts of ice and the excess nitrite is destroyed. A solution of 3.70 parts of the ester of formula (IX) in 25 parts of glacial acetic acid is then added gradually. The precipitate is filtered and rinsed until it is neutral.

In the dispersed form, the dyestuff thus obtained of the formula: ##STR13## has excellent affinity for polyester fibres which it dyes with a shade which is very fast to light and sublimation.

The following Table shows other Examples of dyestuffs according to the invention which have been prepared as in Example 8 by coupling the diazo derivative of the amine of formula (III) indicated in the second column with the ester of formula (IV) defined in the following columns and prepared by the method given in Example 7 using the corresponding alcohol of formula (V) and the corresponding acid chloride of formula (VII). In column Z, the letter o, m or p placed in front of the group represented by Z indicated the position (ortho, meta or para respectively) of Z relative to the ester group.

    __________________________________________________________________________                                                              Shade on                               Ester of formula (IV)                   polyester             Ex. Amine of formula (III)                                                                      n Y   X      R                Z         fibres                __________________________________________________________________________     9   2-amino-5-nitro-benzo-                                                                      2 H   CH.sub.3                                                                              C.sub.2 H.sub.5  p, CH.sub.3 CH(Cl)CN                                                                     ruby                      nitrile                                                                    10  "            " "   "      "                p, CH═CH--ON                                                                         "                     11  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    12  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    13  "            " "   "      "                m, CH.sub.2 CH(Cl)CN                                                                     "                     14  "            " "   NHCOCH.sub.3                                                                          "                o, CH.sub.2 CH(Cl)CN                                                                     reddish-                                                                       blue                  15  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     16  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    17  "            " "   "      "                p, CH.sub.2 CH.sub. 2                                                                    "N                    18  "            " "   Cl     "                o, CH.sub.2 CH(Cl)CN                                                                     red                   19  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     20  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    21  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    22  "            " OCH.sub.3                                                                          CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     violet                23  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     24  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    25  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    26  "            " "   NHCOCH.sub.3                                                                          "                o, CH.sub.2 CH(Cl)CN                                                                     blue                  27  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    28  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     29  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    30  "            " H   H      CH.sub.2 CH.sub.2 CN                                                                            o, CH.sub.2 CH(Cl)CN                                                                     red                   31  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    32  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     33  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    34  "            " "   benzoyl-                                                                              C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                     reddish-                                     amino                             blue                  35  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     36  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    37  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    38  "            " "   H      C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                     bluish-                                                                        red                   39  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     40  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    41  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    42  "            3 "   CH.sub.3                                                                              C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                     ruby                  43  "            " "   "      p, CH.sub.2 CH.sub.2 CN                                                                         "                               44  "            2 "   H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                        o, CH.sub.2 CH(Cl)CN                                                                     bluish-                                                                        red                   45  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    46  "            " "   Cl     CH.sub.2 CH.sub.2 CN                                                                            o, CH.sub.2 CH(Cl)CN                                                                     red                   47  "            " "   "      CH.sub.2 CH.sub.2 CN                                                                            p, CH.sub.2 CH.sub.2                                                                     "N                    48  "            " "   OCH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                     bluish-red            49  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    50  "            " "   H      2-[2-(2-chloro-2-cyanoethyl)-                                                                   o, CH.sub.2 CH(Cl)CN                                                                     red                                                 benzoyloxy]-ethyl                                51  "            " "   "      2-[2-(2-cyanoethyl)-benzoyl-                                                                    o, CH.sub.2 CH.sub.2                                                                     "N                                                  oxy]-ethyl                                       52  "            3 "   CH.sub.3                                                                              2-[4-(2-chloro-2-cyanoethyl)-                                                                   p, CH.sub.2 CH(Cl)CN                                                                     "                                                   benzoyloxy]-ethyl                                53  "            " "   "      2-[4-(2-cyano-ethyl)4-benzoyloxy]-2                                                             p, CH.sub.2 CH.sub.2                                                                     "N                                                  ethyl                                            54  2-chloro-4-  " "   CH.sub.3                                                                              C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                     scarlet                   nitro-aniline                                                              55  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    56  "            2 "   "      "                p, CH═CHCN                                                                           "                     57  "            " "   NHCOCH.sub.3                                                                          "                o, CH.sub.2 CH(Cl)CN                                                                     bluish-                                                                        red                   58  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    59  "            " "   benzoyl-                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     "                                            amino                                                   60  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    61  "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     ruby                  62  2-bromo-4-nitro-                                                               aniline      " H   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     scarlet               63  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    64  "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     ruby                  65  "            " "   benzoyl-                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     "                                            amino                                                   68  2,6-dichloro-4-nitro-                                                          aniline      " H   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     reddish-                                                                       brown                 67  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    68  "            " "   "      "                p, CH═CHCN                                                                           "                     69  "            " "   NHCOCH.sub.3                                                                          "                o, CH.sub.2 CH(Cl)CN                                                                     bordeaux              70  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    71  "            " OCH.sub.3                                                                          benzoyl-                                                                              "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                     amino                             violet                72  "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     73  2,6-dibromo-4-nitro-                                                                        " H   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     reddish-                  aniline                                              brown                 74  "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     75  "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                                                       violet                76  "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     77  "            " "   benzoyl-                                                                              "                p, CH═CHCN                                                                           "                                                   amino                                            78  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                           (Cl)CN    "                     79  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    80  "            " "   "      "                o, CH.sub. 2 CH.sub.2                                                                    "N                    81  4-nitro-aniline                                                                             " H   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     scarlet               82  "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    83  "            " "   NHCOCH.sub.3                                                                          "                o, CH.sub.2 CH(Cl)CN                                                                     red                   84  "            " "NHCOCH.sub.3                                                                      "      p, CH═CHCN   "                               85  "            " "   benzoyl-                                                                       amino  "                p, CH.sub.2 CH.sub.2                                                                     "N                    86  "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     87  "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     bluish                                                                         red                   88  2,4-dinitro-6-bromo-                                                           aniline      " H   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     violet                89  "            " "   "      "                p, CH═CHCN                                                                           violet                90  "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     91  "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     92  "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                                                       blue                  93  "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     94  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    95  "            " "   "      benzoyl-                                                                amino  "                p, CH.sub.2 CH.sub.2                                                                     "N                    96  "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    97  "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     navy blue             98  "            " "   "      "                p, CH═CHCN                                                                           "                     99  2,4-dinitro-6-chloro-                                                          aniline      " H   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     bluish                                                                         violet                100 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    101 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                                                       blue                  102 "            " "   "      "                m, CH═CHCN                                                                           "                     103 "            " "   benzoyl-                                                                              "                o, CH.sub.2 CH.sub.2                                                                     "N                                           amino                                                   104 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    105 "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     navy blue             106 2-amino-3,5-dinitro-                                                           benzonitrile " H   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                                             blue                            107 "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     108 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     blue                  109 "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     110 "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     111 "            " "   benzoyl-                                                                              "                p, CH.sub.2 CH.sub.2                                                                     "N                                           amino-                                                  112 "            " OCH.sub.3                                                                          "      "                p, CH.sub.2 CH.sub.2                                                                     greenish-                                                                      blue                  113 "            " "   "      "                p, CH═CHCN                                                                           "                     114 4-amino-azobenzene                                                                          " H   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     orange                115 "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     116 "            " "   NHCOCH.sub.3                                                                          "                p, CH═CHCN                                                                           scarlet               117 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    118 "            " "   benzoyl-                                                                       amino  "                m, CH.sub.2 CH.sub.2                                                                     "N                    119 "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     120 2-amino-5-nitro-                                                               thiazole     " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     reddish-                                                                       blue                  121 "            " "   "      "                p, CH.sub.2 CH(Cl)CN                                                                     "                     122 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                                                       blue                  123 "            " "   "      "                p, CH═CHCN                                                                           "                     124 "            " "   "      "                o, CH.sub.2 CH.sub.2                                                                     "N                    125 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     blue                  126 "            " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     "                     127 "            " "   benzoyl-                                                                       amino  "                p, CH.sub.2 CH.sub.2                                                                     "N                    128 "            " "   "      "                m, CH.sub.2 CH(Cl)CN                                                                     "                     129 "            " OCH.sub.3                                                                          NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     greenish-                                                                      blue                  130 3-methyl-4-nitro-                                                              5-amino-isothiazole                                                                         " H   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     ruby                  131 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    132 2-amino-6-carbethoxy-                                                          benzothiazole                                                                               " "   "      "                o, CH.sub.2 CH(Cl)CN                                                                     red                   133 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     ruby                  134 "            " "   benzoyl-                                                                       amino  "                p, CH.sub.2 CH.sub.2                                                                     "N                    135 2-amino-6-thiocyano-                                                           benzothiazole                                                                               " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     bluish-                                                                        red                   136 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     reddish-                                                                       violet                137 "            " "   benzoyl-                                                                       amino  "                m, CH═CHCN                                                                           "                     138 2-amino-6-methylsul-                                                                        " "   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     ruby                      fonyl-benzothiazole                                                        139 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     violet                140 "            " "   benzoyl-                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     "                                            amino                                                   141 2-amino-6-cyano-                                                               benzothiazole                                                                               " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     red                   142 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     ruby                  143 "            " "   benzoyla-                                                                             "                p, CH.sub.2 CH.sub.2                                                                     "N                                           mino                                                    144 2-amino-6-nitro-benzo-                                                         thiazole     " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     bluish-                                                                        red                   145 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     violet                146 "            " "   benzoyl-                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     "                                            amino                                                   147 2-methylsulfonyl-4-                                                            nitro-aniline                                                                               " "   CH.sub.3                                                                              "                m, CH.sub.2 CH(Cl)CN                                                                     ruby                  148 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     violet                149 "            " "   benzoyl-                                                                       amino  "                p, CH.sub.2 CH.sub.2                                                                     "N                    150 2-chloro-4-methyl-                                                             sulfonyl-aniline                                                                            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH(Cl)CN                                                                     red                   151 2-nitro-4-methyl-                                                                           " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     "                         sulfonyl-aniline                                                           152 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     ruby                  153 3-amino-5-nitro-                                                               benzisothiazole-2,1                                                                         " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     blue                  154 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     greenish-                                                                      blue                  155 "            " "   benzoyl-                                                                       amino  "                p, CH.sub.2 CH.sub.2                                                                     "N                    156 2-amino-5-nitro-                                                                            " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     scarlet                   thiadiazole-1,3,4                                                          157 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     red                   158 3-methylsulfonyl-5-amino                                                       thiadiazole-1,2,4                                                                           " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     "                     159 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     bluish-red            160 3-phenyl-5-amino-                                                              thiadiazole-1,2,4                                                                           " "   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     red                   161 "            " "   NHCOCH.sub.3                                                                          "                o, CH.sub.2 CH(Cl)CN                                                                     bluish-                                                                        red                   162 2-amino-3-chloro-5-                                                            nitro benzonitrile                                                                          " "   CH.sub.3                                                                              "                o, CH.sub.2 CH(Cl)CN                                                                     violet                163 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     bluish-                                                                        violet                164 2-amino-3-bromo-5-                                                             nitro benzonitrile                                                                          " "   CH.sub.3                                                                              "                p, CH═CNCN                                                                           violet                165 "            " "   NHCOCH.sub.3                                                                          "                p, CH.sub.2 CH.sub.2                                                                     bluish-                                                                        violet                166 2-carbethoxy-4-nitro-                                                          aniline      " "   "      "                p, CH.sub.2 CH.sub.2                                                                     ruby                  167 "            " "   CH.sub.3                                                                              "                p, CH.sub.2 CH.sub.2                                                                     red                   168 2-amino-5-nitro-benzo-                                                         nitrile      " "   H      C.sub.2 H.sub.4 OCO--                                                                           o, CH.sub.2 CH.sub.2                                                                     ruby                                                CH.sub.3                                         169 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    170 "            " "   "      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                               o, CH.sub.2 CH.sub.2                                                                     "N                    171 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    172 "            " "   "      C.sub.2 H.sub.4 OH                                                                              o, CH.sub.2 CH.sub.2                                                                     "N                    173 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    174 "            " "   "      C.sub.2 H.sub.4 OCH.sub.3                                                                       p, CH.sub.2 CH.sub.2                                                                     "N                    175 "            " "   "      C.sub.2 H.sub.4 SO.sub.2 '                                                     CH.sub.3         o, CH.sub.2 CH.sub.2                                                                     red                   176 "            " "   "      C.sub.2 H.sub.4 OCO.sub.2 --                                                                    o, CH.sub.2 CH.sub.2                                                                     ruby                                                CH.sub.3                                         177 "            " "   "      phenoxy-         p, CH.sub.2 CH.sub.2                                                                     "N                                                  ethyl                                            178 2-amino-3-nitro-5-                                                                          " "   CH.sub.3                                                                              C.sub.2 H.sub.5  o, CH.sub.2 CH.sub.2                                                                     blue                      acetyl-thiophene                                                           179 "            " "   "      "                p, CH.sub.2 CH.sub.2                                                                     "N                    180 2-amino-5-nitro-                                                                            " OC.sub.2 H.sub.5                                                                   "      "                o, CH.sub.2 CH.sub.2                                                                     violet                    benzonitrile                                                               181 "            " CH.sub.3                                                                           "      "                o, CH.sub.2 CH.sub.2                                                                     ruby                  182 "            " C.sub.2 H.sub.5                                                                    H      "                "         "                     183 "            " H   C.sub.2 H.sub.5                                                                       "                "         "                     184 "            " "   OC.sub.2 H.sub.5                                                                      CH.sub.2 CH.sub.2 CN                                                                            "         bluish-                                                                        red                   185 "            " "   NH--CHO                                                                               C.sub.2 H.sub.5  "         reddish-                                                                       blue                  186 "            " "   NHCOC.sub.2A H.sub.5                                                                  "                o, CH.sub.2 CH.sub.2                                                                     "N                    187 "            " "   cinnamoyl-                                                                     amino  "                "         "                     188 3-chloro-4-amino-                                                                           " "   CH.sub.3                                                                              "                "         scarlet                   azobenzene                                                                 189 3-bromo-4-amino-                                                                            " "   "      "                "         "                         azobenzene                                                                 190 3,5-dichloro-4-amino-                                                                       " "   "      "                "         reddish-                  azobenzne                                            brown                 191 3,5-dibromo-4-amino-                                                                        " "   "      "                "         "                         azobenzene                                                                 192 4-amino-2-methyl-                                                                           " "   "      "                "         orange                    azobenzene                                                                 193 4-amino-2-ethyl-                                                                            " "   "      "                "         "                         azobenzene                                                                 194 4-amino-2-methoxy-                                                                          " "   "      "                "         reddish-                  azobenezene                                          orange                195 4-amino-2-ethoxy-                                                                           " "   "      "                "         "                         azobenzene                                                                 196 2,4-dinitro-6-chloro-                                                                       " "   "      "                "         bluish-                   aniline                                              violet                197 2,6-dichloro-4-nitro-                                                                       " "   "      "                "         reddish-                  aniline                                              brown                 __________________________________________________________________________

EXAMPLE 198

5.5 parts of 2-cyano-4-nitro 2'-methyl-4'-[N-ethyl-N-(hydroxy-ethyl)amino] azobenzene, obtained by coupling the diazo derivative of 2-amino-5-nitrobenzonitrile with N-ethyl-N-hydroxyethyl metatoluidine, are dissolved in 50 parts of pyridine. 2.5 parts of 2-(2-chloro-2-cyanoethyl) benzoyl chloride are added slowly, then the mixture is heated at 40°-50° C. for 30 minutes. The dyestuff is salted out by simply diluting the mixture with 250 parts of water, acidifying the mixture by means of hydrochloric acid up to pH 3-4 and by the temperature being maintained at 10° C. to 15° C. The dyestuff thus obtained is identical with that in Example 8.

EXAMPLE 199

A fabric of ethylene glycol polyterephthalate fibres is printed with a printing paste containing 20 parts of the dyestuff of Example 11, 150 parts of a solid salt of sulphonated castor oil, 600 parts of a thickening agent and 250 parts of water. After being dried, the fabric is thermofixed for one minute at 200° C. and then subjected to a reducing treatment with sodium dithionate. A ruby shade having very good general fastness is obtained.

EXAMPLE 200

A fabric of ethylene glycol polyterephthalate fibres is foularded in a bath comprising 9 parts of the dyestuff of Example 100, 0.5 parts of a polyglycol ether of oleic alcohol, 1.5 parts of a polyacrylamide and 989 parts of water. After it has been dried, the fabric is thermofixed for 1 minute at 200° C. and then subjected to a reducing treatment with sodium dithionate. A violet shade is obtained with very good general fastness. 

We claim:
 1. A dyestuff of the formula: ##STR14## in which A is thiazolyl, isothiazolyl, benzothiazolyl, benzisothiazolyl, thiadiazolyl, thienyl, or imidazolyl which is unsubstituted or substituted by one to three substituents selected from chlorine, bromine, methyl, phenyl, nitro, cyano, thiocyano, acetyl, carbalkoxy containing 2 to 5 carbon atoms and alkylsulfonyl containing 1 to 4 carbon atoms;X is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, formylamino, acetylamino, propanoylamino, benzoylamino or cinnamoylamino; Y is hydrogen, methyl, ethyl, methoxy or ethoxy; R is hydrogen, alkyl containing 1 to 4 carbon atoms or the group of formula: ##STR15## said alkyl being unsubstituted or substituted by one hydroxy, alkoxy containing 1 to 4 carbon atoms, phenoxy, acetyloxy, cyano, alkylsulfonyl containing 1 to 4 carbon atoms, carbalkoxy containing 2 to 5 carbon atoms or alkoxycarbonyloxy containing 2 to 5 carbon atoms; n is equal to 1, 2, or 3; and Z is 2-cyanovinyl, 2-cyanoethyl or 2-chloro-2-cyanoethyl.
 2. Dyestuff as claimed in claim 1 wherein n is equal to
 2. 3. A dyestuff as claimed in claim 1, in which A is 5-nitro-2-thiazolyl, 3-methyl-4-nitro-5-isothiazolyl, 6-carbethoxy-2-benzothiazolyl, 6-thiocyano-2-benzothiazolyl, 6-methylsulfonyl-2-benzothiazolyl, 6-cyano-2-benzothiazolyl, 6-nitro-2-benzothiazolyl, 5-nitro-2,1-benzothiazol-3-yl, 5-nitro-1,3,4-thiadiazol-2-yl, 3-methylsulfonyl-1,2,4-thiadiazol-5-yl, 3-phenyl-1,2,4-thiadiazol-5-yl or 3-nitro-5-acetyl-2-thienyl.
 4. Dyestuff as claimed in claim 1 wherein, Y is hydrogen, X is hydrogen, chlorine, methyl or acetylamino, R is ethyl or β-cyanoethyl and n is
 2. 5. A dyestuff of the formula: ##STR16## wherein A, n and Z are as defined in claim
 1. 6. The dyestuff of the formula: ##STR17## 